EP0992477A1 - Verfahren zur Herstellung von Citral - Google Patents
Verfahren zur Herstellung von Citral Download PDFInfo
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- EP0992477A1 EP0992477A1 EP99118458A EP99118458A EP0992477A1 EP 0992477 A1 EP0992477 A1 EP 0992477A1 EP 99118458 A EP99118458 A EP 99118458A EP 99118458 A EP99118458 A EP 99118458A EP 0992477 A1 EP0992477 A1 EP 0992477A1
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- formula
- citral
- column
- acetal
- prenol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/515—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an acetalised, ketalised hemi-acetalised, or hemi-ketalised hydroxyl group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
Definitions
- the present invention relates to an improved method for Preparation of 3,7-dimethyl-octa-2,6-dien-1-al (citral) by thermal cleavage of 3-methyl-2-buten-1-al-diprenylacetal.
- Citral is used as a fragrance and is also considered a Starting material for other fragrances, such as geraniol, and as Starting material for vitamins, for example vitamin A, from great importance.
- a disadvantage of the described, in itself very good process is that the process is only for batch processing is suitable and long residence times (about 6 hours) and therefore requires large equipment.
- Another disadvantage of the known The procedure is that in the system an adjuvant, namely the intermediate boiler, must be introduced, which is an additional Effort for dosing the auxiliary, for monitoring the concentration of the excipient and for the separation of the auxiliary means.
- the invention accordingly relates to a process for the preparation of 3,7-dimethyl-2,6-octadien-1-al (citral) of the formula I. by thermal cleavage, if appropriate in the presence of an acidic catalyst of 3-methyl-2-buten-1-al-diprenylacetal of the formula II with the elimination of 3-methyl-2-buten-1-ol (prenol) of the formula III to the cis / trans-prenyl (3-methyl-butadienyl) ether of the formula IV
- the method according to the invention succeeds with particular advantage if the thermal cleavage of the acetal of formula II in lower part or in the bottom of a functioning as a column Distillation column with 5 to 100 theoretical plates carries out.
- One way of carrying out the process according to the invention is characterized in that the thermal cleavage of the acetal of the formula II is carried out in the lower part or in the bottom of a distillation column with 5 to 100 theoretical plates, the acetal of the formula II being selected by suitable selection of the distillation conditions in bottom part or in the bottom of the column, the citral of formula I, the intermediate intermediates of formulas IV and V and the split off prenol of formula III together at the top of the column as a top stream and the mixture of citral and the intermediates of Pass formulas IV and V before or after separation of prenol and any by-products by distillation through a heated residence tube (7) in which the intermediates of formulas IV and V are rearranged to cital at temperatures of 100 to 200 ° C.
- the process according to the invention is particularly advantageous if the thermal cleavage of the acetal of the formula II is carried out in the lower part (9) or in the bottom (10) of a distillation column (1) with 5 to 100 theoretical plates, with the acetal of the formula II by suitable selection of the distillation conditions in the lower part (9) or in the bottom (10) of the column (1), the citral of the formula I formed and the intermediately formed intermediates of the formulas IV and V together on one in the middle or lower part withdrawn from the column arranged side draw (5) in liquid or vapor form and the cleaved prenol of the formula III is separated off at the top (8) of the column with the top stream.
- the acetal required as the starting compound can, for example described in EP 0 021 074 B1, quite simply by implementation of 3-methyl-2-buten-1-ol (prenol) with 3-methyl-2-buten-1-al (Prenal).
- Prenal 3-methyl-2-buten-1-ol
- Prenal 3-methyl-2-buten-1-al
- Depending on the manufacturing conditions of the acetal can be between 0.1 and 30% by weight unreacted Prenal and between 0.1 and 60 wt .-% of not contain implemented Prenol.
- Advantageous for the invention It is used when the concentration of the process Acetals of formula II in the starting material over 30 wt .-%,
- the cleavage of the acetal of formula II to prenol, citral and The citral precursors of the formulas IV and V take place in one Distillation column, the so-called column (1), with an evaporator (2) and a condenser (3). Trays and packing are suitable as internals (4) for the column and in particular structured packings made of sheet metal (e.g. Sulzer 250.Y) or metal mesh (e.g. Sulzer BX or Sulzer CY). The The number of theoretical plates in the column should be between 5 and 100. In a preferred embodiment of the invention there is a side trigger (5) from which the citral and the Citral precursors in vapor or liquid form from the Column are removed.
- a side trigger (5) from which the citral and the Citral precursors in vapor or liquid form from the Column are removed.
- the side trigger (5) is in the middle or lower part of the column (1), the side draw (5) useful between 2 and 20 theoretical plates lies above the addition point (6) of the acetal. Above the Side deduction (5) are still between 2 and 80 theoretical Separation stages.
- the mixture of citral and the citral precursors is passed through a heated retention tube (7) in which the Citral precursors of formulas IV and V are thermally rearranged to citral become.
- the citral obtained can then be taken from the sampling point (11) can be removed.
- Prenol recovered from the top stream in the condenser (3) and possibly 3-methyl-2-buten-1-al can be taken at the withdrawal point (12) removed and again for the preparation of the acetal of formula II be returned to the process.
- the one in the process accumulating relatively small amounts of sump drain can the removal point (13) can be removed.
- the acetal is preferred in the lower part of the column (1) but in the bottom (10) of the column (1) or in the evaporator (2) added. If necessary, the sump (10) Fission column through a container to be enlarged to have a larger reaction volume available.
- the inflow at the acetal of formula II is appropriately such that the the inflow of acetal based residence time between one minute and 6 hours, preferably between 5 minutes and 2 hours. This relatively short dwell time and the effects caused by it small, less expensive devices represent a clear one Advantage of the method according to the invention.
- the process can be discontinuous, semi-continuous or be carried out continuously.
- the semi-continuous Procedural management becomes a at the beginning of the implementation submitted certain amount of acetal and then optionally added more acetal.
- the device can be started in the sump Column, a high-boiling inert compound are presented, to ensure a minimum level of the sump and the evaporator.
- All inert under the reaction conditions are suitable liquids that have a higher boiling point than citral and in particular as the acetal of formula II, such as Example the hydrocarbons tetradecane, pentadecane, hexadecane, Octadecane, eicosane, or ethers, such as diethylene glycol dibutyl ether, White oils, paraffin oils or mixtures of the above Links.
- the reaction can be carried out without a catalyst, i.e. only by heating, be performed. However, it will be of particular advantage made in the presence of an acid catalyst.
- sour Catalysts are in particular non-volatile protonic acids such as sulfuric acid, p-toluenesulfonic acid and above all Suitable phosphoric acid.
- the catalyst is advantageously in the lower part of the column (1), preferably in the bottom of the column or in added the evaporator (2).
- the concentration of the catalyst in the reaction mixture is expediently between 0.0001% and 1% by weight, preferably 0.0005 and 0.5 wt .-%, based on the total amount of the reaction mixture.
- the catalyst can be in pure form or dissolved in be added to a suitable solvent.
- a solvent for the catalyst are water, alcohols and hydrocarbons, but preferably those present in the reaction mixture Compounds such as prenol, 3-methyl-2-butenal, citral, the citral precursors of formulas IV and V and in particular that Acetal of formula II suitable. If water is used, it should whose concentration in the reaction mixture should be as low as possible, since water backreacts the acetal to prenol and 3-methyl-2-butenal causes. For the other solvents, it is advisable when the concentration of the catalyst in the solvent is between 0.01% and 50% by weight.
- the pressure in the bottom of the column is advantageously between 1 mbar and 100 mbar, in particular between 10 and 70 mbar.
- the temperature in the bottom of the column is generally between 70 ° C. and 270 ° C, preferably between 100 ° C and 220 ° C, in particular between 130 ° C and 190 ° C.
- the reflux ratio at the top of the column is advantageous between 0.5 and 70, in particular between 2 and 30.
- the amount of sump drain is extremely small and lies less than 10% by weight, often even less than 5% by weight of the added acetals since almost all of the added acetals Formula II is split into valuable products and only a very small one Part of the reactants reacted to high-boiling by-products. This high selectivity also represents a great advantage of the method according to the invention.
- the distillate obtained at the top of the column consists essentially from the valuable products prenol, 3-methyl-2-butenal, citral and the citral precursors of formulas IV and V.
- This mixture can easily by distillation, for example by distillation in another column, in Prenol and possibly from the Preparation of the unreacted acetal of the formula II 3-methyl-2-butenal and in citral and the citral precursors of Formulas IV and V are separated. It is also possible to use the in this mixture contained citral precursors by heating Relocate temperatures between 100 ° C and 200 ° C in citral and then separate the citral by distillation.
- the recovered Compounds prenol and possibly 3-methyl-2-butenal can again can be used to prepare the acetal of formula II.
- the inventive method with a column a side deduction.
- an additional Distillation column can be dispensed with.
- the head trigger of the The splitting column then essentially consists of Prenol and possibly 3-methyl-2-butenal, which is readily used again to produce the Acetals of formula II can be used.
- the one through the Lateral deduction product stream consists of more than 70 wt .-% and often even more than 85% by weight of citral and the citral precursors of formulas IV and V.
- Citral precursors are known to be heated rearranged to temperatures between 100 ° C and 200 ° C in citral.
- the apparatus consisted of an electrically heated 1 liter flask with an attached column, which was equipped with an electric reflux divider (to achieve a reflux ratio of 1: 1).
- the column was filled with a 1m high Sulzer EX packing.
- the flask was filled with 500 g of a 90% by weight acetal of the formula II.
- examples 1 and 3 up to 31 ppm phosphoric acid was added as a catalyst.
- no catalyst was added.
- the top pressure of the column was between 5 and 60 mbar. After heating the contents of the flask, 3-methyl-2-butenediprenylacetal was pumped in continuously between 100 g / h and 200 g / h.
- the cleavage products (mainly Prenol) and the citral precursors cis / trans-prenyl- (3-methyl-butadienyl) ether of the formula IV and 2,4,4-trimethyl-3-formyl-1,5-hexadiene of the formula V were continuously distilled off and collected.
- the acetal was retained in the reaction flask by refluxing and regulating the heating power. After the end of the experiment, the distillate and the contents of the flask were weighed out and analyzed by gas chromatography.
- the parameters and results of Examples 1 to 3 are in the table 1 compiled.
- Example 1 Example 2 Inflow of acetal [ml / h] 100 100 200 Pressure at the top of the column [mbar] 6 60 5 Pressure in the piston [mbar] 20th 70 23 Temperature in the flask [° C] 143 to 148 169 to 190 143 to 148 Weighing in acetal [g] 507.8 503 507.3 Concentration of H 3 PO 4 in the flask [ppm] 31 without 27.2 Acetal (filling + inflow) [g] 891.3 1107.8 1485.2 Inflow amount of acetal [g] 383.5 604.8 977.9 Distillate [g] 711.9 958.4 1174.7 Swamp after the end of the test [g] 172.2 153.3 312.7 Sales of acetal 83.1% 97.4% 49.8% Selectivity to prenol 98.7% 95.2% 92.7% Selectivity to citral and citral precursors 89.1% 96.0% 97.8%
- Example 2 The parameters and results of Examples 4 to 8 are summarized in Table 2.
- the apparatus consisted of a column with 30 theoretical plates. The bottom of the column was heated with a falling film evaporator. The side draw for the citral and the citral precursors was located 10 separation levels above the sump. The distillate condensing at the top of the column was collected and part of it was pumped back to the top of the column as a reflux. 100 g of acetal of the formula II were added to the bottom of the column per hour. As a catalyst, an approximately 1% by weight solution of H 3 PO 4 in the acetal of the formula II was added to the bottom of the column. The amount of catalyst solution was measured so that the concentration of H 3 PO 4 given in the table in the bottom of the column was obtained.
- the selectivity to Prenol was greater than 89.3%.
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Mit besonderem Vorteil gestaltet sich das erfindungsgemäße Verfahren, wenn man die thermische Spaltung des Acetals der Formel II im unteren Teil (9) oder im Sumpf (10) einer Destillationskolonne (1) mit 5 bis 100 theoretischen Trennstufen durchführt, wobei man das Acetal der Formel II durch geeignete Auswahl der Destillationsbedingungen im unteren Teil (9) bzw. im Sumpf (10) der Kolonne (1) hält, das gebildete Citral der Formel I und die intermediär gebildeten Zwischenprodukte der Formeln IV und V gemeinsam an einem im mittleren oder unteren Teil der Kolonne angeordneten Seitenabzug (5) flüssig oder dampfförmig abzieht und das abgespaltene Prenol der Formel III am Kopf (8) der Kolonne mit dem Kopfstrom abtrennt.
Beispiel 1 | Beispiel 2 | Beispiel 2 | |
Zufluß an Acetal [ml/h] | 100 | 100 | 200 |
Druck am Kolonnenkopf[mbar] | 6 | 60 | 5 |
Druck im Kolben [mbar] | 20 | 70 | 23 |
Temperatur im Kolben [°C] | 143 bis 148 | 169 bis 190 | 143 bis 148 |
Einwaage an Acetal [g] | 507,8 | 503 | 507,3 |
Konzentration an H3PO4 im Kolben [ppm] | 31 | ohne | 27,2 |
Acetal (Füllung + zugeflossen) [g] | 891,3 | 1107,8 | 1485,2 |
Zugeflossene Menge an Acetal [g] | 383,5 | 604,8 | 977,9 |
Destillat [g] | 711,9 | 958,4 | 1174,7 |
Sumpf nach Versuchsende [g] | 172,2 | 153,3 | 312,7 |
Umsatz des Acetals | 83,1% | 97,4 % | 49,8 % |
Selektivität zu Prenol | 98,7 % | 95,2 % | 92,7 % |
Selektivität zu Citral und Citralvorstufen | 89,1% | 96,0 % | 97,8 % |
Beispiel | 4 | 5 | 6 | 7 | 8 |
H3PO4-Konzentration [ppm] | 117 | 475 | 332 | 269 | 1044 |
Temperatur im Sumpf[°C] | 175 | 145 | 155 | 160 | 150 |
Druck am Kolonnenkopf [mbar] | 50 | 30 | 30 | 30 | 50 |
Rückflußmenge [g/h] | 968 | 774 | 968 | 774 | 774 |
Acetalkonz. im Zufluß [kg/kg] | 83,94 % | 76,93 % | 76,93 % | 88,25 % | 85,82 % |
Sumpfabzug [g/h] | 0,37 | 33,51 | 6,82 | 0,51 | 6,91 |
Seitenabzug [g/h] | 57,00 | 29,76 | 47,33 | 61,74 | 52,13 |
Kopfabzug [g/h] | 42,80 | 38,26 | 48,84 | 35,22 | 40,44 |
Rückflußverhältnis | 23 | 20 | 20 | 22 | 19 |
Inhalt des Sumpfes [g] | 100 | 100 | 100 | 170 | 170 |
Umsatz des Acetals | 99,5% | 67,5 % | 95,3 % | 99,8 % | 99,3 % |
Selektivität zu Citral und Citralvorstufen | 91,8 % | 96,6 % | 90,0 % | 93,4 % | 97,6 % |
Claims (10)
- Verfahren zur Herstellung von 3,7-Dimethyl-2,6-octadien-1-al (Citral) der Formel I durch thermische Spaltung ggf. in Gegenwart eines sauren Katalysators von 3-Methyl-2-buten-1-al-diprenylacetal der Formel II unter Abspaltung von 3-Methyl-2-buten-1-ol (Prenol) der Formel III zu cis/trans-Prenyl-(methyl-butadienyl)-ether der Formel IV Claisen-Umlagerung des erhaltenen Butadienylethers der Formel IV zu 2,4 4-Trimethyl-3-formyl-1,5-hexadien der Formel V und anschließende Cope-Umlagerung desselben zum Citral der Formel I, dadurch gekennzeichnet, daß man sowohl das gebildete Prenol der Formel III, als auch die intermediär gebildeten Zwischenprodukte der Formeln IV und V und das Citral schon während der Umsetzung fortlaufend destillativ aus dem Reaktionsgemisch entfernt und die Zwischenprodukte der Formeln IV und V vor oder nach destillativer Abtrennung von Prenol und ggf. Nebenprodukten durch Erhitzen auf Temperaturen zwischen 100 und 200°C in Citral umlagert.
- Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß man die thermische Spaltung des Acetals der Formel II im unteren Teil oder im Sumpf einer Destillationskolonne mit 5 bis 100 theoretischen Trennstufen durchführt.
- Verfahren gemäß Anspruch 2, dadurch gekennzeichnet, daß man das Acetal der Formel II und ggf. den sauren Katalysator in den unteren Teil der Kolonne, in den Sumpf der Kolonne oder in den Verdampfer (2) der Kolonne einbringt.
- Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß man die thermische Spaltung des Acetals der Formel II im unteren Teil oder im Sumpf einer Destillationskolonne mit 5 bis 100 theoretischen Trennstufen durchführt, wobei man das Acetal der Formel II durch geeignete Auswahl der Destillationsbedingungen im unteren Teil bzw. im Sumpf der Kolonne hält, das gebildete Citral der Formel I, die intermediär gebildeten Zwischenprodukte der Formeln IV und V und das abgespaltene Prenol der Formel III gemeinsam am Kopf der Kolonne als Kopfstrom gewinnt und das Gemisch aus Citral und den Zwischenprodukten der Formeln IV und V vor oder nach destillativer Abtrennung von Prenol und ggf. Nebenprodukten durch ein beheiztes Verweilzeitrohr (7) führt, in dem die Zwischenprodukte der Formeln IV und V bei Temperaturen von 100 bis 200°C zu Cital umgelagert werden.
- Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß man die thermische Spaltung des Acetals der Formel II im unteren Teil (9) oder im Sumpf (10)einer Destillationskolonne (1) mit 5 bis 100 theoretischen Trennstufen durchführt, wobei man das Acetal der Formel II durch geeignete Auswahl der Destillationsbedingungen im unteren Teil (9) bzw. im Sumpf (10) der Kolonne (1) hält, das gebildete Citral der Formel I und die intermediär gebildeten Zwischenprodukte der Formeln IV und V gemeinsam an einem im mittleren Teil der Kolonne angeordneten Seitenabzug (5) flüssig oder dampfförmig abzieht und das abgespaltene Prenol der Formel III am Kopf (8) der Kolonne mit dem Kopfstrom abtrennt.
- Verfahren gemäß Anspruch 5, dadurch gekennzeichnet, daß man das an dem Seitenabzug (5) abgezogene Gemisch aus Citral und den intermediär gebildeten Zwischenprodukten der Formeln IV und V durch ein beheiztes Verweilzeitrohr (7) führt, in dem die Zwischenprodukte der Formeln IV und V bei Temperaturen von 100 bis 200 °C zu Citral umgelagert werden.
- Verfahren gemäß Anspruch 5, dadurch gekennzeichnet, daß man die Herstellung des Citrals kontinuierlich durchführt.
- Verfahren gemäß Anspruch 5, dadurch gekennzeichnet, daß sich der Seitenabzug (5) 2 bis 20 theoretische Trennstufen oberhalb der Zugabestelle (6) für das Acetal der Formel II und 2 bis 80 theoretische Trennstufen unterhalb des Kolonnenkopfes (8) befindet.
- Verfahren gemäß Anspruch 2, dadurch gekennzeichnet, daß der Druck im Sumpf der Kolonne zwischen 1 und 100 mbar beträgt und die Temperatur im Sumpf der Kolonne zwischen 70 und 270 °C beträgt.
- Verfahren gemäß Anspruch 2, dadurch gekennzeichnet, daß das Rücklaufverhältnis am Kopf der Destillationskolonne zwischen 0,5 und 70.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SI9930238T SI0992477T1 (en) | 1998-10-07 | 1999-09-17 | Process for the preparation of citral |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19846056 | 1998-10-07 | ||
DE19846056A DE19846056A1 (de) | 1998-10-07 | 1998-10-07 | Verfahren zur Herstellung von Citral |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0992477A1 true EP0992477A1 (de) | 2000-04-12 |
EP0992477B1 EP0992477B1 (de) | 2003-02-05 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP99118458A Expired - Lifetime EP0992477B1 (de) | 1998-10-07 | 1999-09-17 | Verfahren zur Herstellung von Citral |
Country Status (10)
Country | Link |
---|---|
US (1) | US6175044B1 (de) |
EP (1) | EP0992477B1 (de) |
JP (1) | JP4980506B2 (de) |
CN (1) | CN1142899C (de) |
AT (1) | ATE232193T1 (de) |
DE (2) | DE19846056A1 (de) |
DK (1) | DK0992477T3 (de) |
ES (1) | ES2192006T3 (de) |
PT (1) | PT992477E (de) |
SI (1) | SI0992477T1 (de) |
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CN111018682A (zh) * | 2019-12-17 | 2020-04-17 | 南通天泽化工有限公司 | 一种柠檬醛的制备方法 |
WO2024002503A1 (de) | 2022-06-30 | 2024-01-04 | Symrise Ag | Verfahren zur herstellung von riech- und duftstoffen am dünnschichtverdampfer |
WO2024068852A1 (en) | 2022-09-28 | 2024-04-04 | Basf Se | Improved process for the preparation of 3,7-dimethyl-octa-2,6-dienal |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0021074A1 (de) * | 1979-06-30 | 1981-01-07 | BASF Aktiengesellschaft | Verfahren zur Herstellung von Citral |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH597123A5 (de) * | 1973-03-12 | 1978-03-31 | Hoffmann La Roche | |
US4016212A (en) | 1973-03-12 | 1977-04-05 | Hoffmann-La Roche Inc. | Process for the preparation of aldehydes |
FR2656604B1 (fr) * | 1990-01-03 | 1992-03-20 | Rhone Poulenc Sante | Procede de preparation du citral. |
JPH11116525A (ja) * | 1997-10-06 | 1999-04-27 | Kuraray Co Ltd | 不飽和カルボニル化合物の製造方法 |
-
1998
- 1998-10-07 DE DE19846056A patent/DE19846056A1/de not_active Withdrawn
-
1999
- 1999-09-17 PT PT99118458T patent/PT992477E/pt unknown
- 1999-09-17 EP EP99118458A patent/EP0992477B1/de not_active Expired - Lifetime
- 1999-09-17 DE DE59904210T patent/DE59904210D1/de not_active Expired - Lifetime
- 1999-09-17 SI SI9930238T patent/SI0992477T1/xx unknown
- 1999-09-17 ES ES99118458T patent/ES2192006T3/es not_active Expired - Lifetime
- 1999-09-17 DK DK99118458T patent/DK0992477T3/da active
- 1999-09-17 AT AT99118458T patent/ATE232193T1/de not_active IP Right Cessation
- 1999-09-24 US US09/404,548 patent/US6175044B1/en not_active Expired - Lifetime
- 1999-10-05 JP JP28441399A patent/JP4980506B2/ja not_active Expired - Lifetime
- 1999-10-07 CN CNB991239318A patent/CN1142899C/zh not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0021074A1 (de) * | 1979-06-30 | 1981-01-07 | BASF Aktiengesellschaft | Verfahren zur Herstellung von Citral |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008037693A1 (de) * | 2006-09-26 | 2008-04-03 | Basf Se | Kontinuierliches verfahren zur herstellung von citral |
US8282793B2 (en) | 2007-06-26 | 2012-10-09 | Basf Se | Continuous process for preparing neral in pure or enriched form |
US8318985B2 (en) | 2007-11-30 | 2012-11-27 | Basf Se | Method for producing optically active, racemic menthol |
US9988331B2 (en) | 2007-11-30 | 2018-06-05 | Basf Se | Method for producing optically active, racemic menthol |
CN113563173A (zh) * | 2021-08-03 | 2021-10-29 | 万华化学集团股份有限公司 | 一种柠檬醛的制备方法 |
CN113563173B (zh) * | 2021-08-03 | 2022-07-12 | 万华化学集团股份有限公司 | 一种柠檬醛的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
SI0992477T1 (en) | 2003-06-30 |
DE59904210D1 (de) | 2003-03-13 |
PT992477E (pt) | 2003-06-30 |
EP0992477B1 (de) | 2003-02-05 |
CN1255480A (zh) | 2000-06-07 |
DE19846056A1 (de) | 2000-04-13 |
ES2192006T3 (es) | 2003-09-16 |
DK0992477T3 (da) | 2003-02-24 |
JP4980506B2 (ja) | 2012-07-18 |
ATE232193T1 (de) | 2003-02-15 |
US6175044B1 (en) | 2001-01-16 |
JP2000119211A (ja) | 2000-04-25 |
CN1142899C (zh) | 2004-03-24 |
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